TWI351417B - The processes of high efficient of disperse the we - Google Patents

Description

1351417 IX. Description of the invention: [Technical field to which the invention pertains] The present invention is applied to a water-retaining resin which is well absorbed in an aqueous solution, and is widely used in agricultural or horticultural water retaining agents, construction materials, anti-dew In addition to the water side of the oil towel, or the outer layer in the cable = water coating agent and sanitary products such as diapers, feminine hygiene products, disposable holdings; The above-mentioned high-yield tree test polymerization money is still touched and then twisted and smashed (4) (4) in the dry ray towel, when it is scattered, it will cause incomplete drying, thereby reducing the efficiency of the whole process, for drying efficiency, The high drying temperature will be high, and the drying temperature will increase, such as: particle size, tea bag retention, absorption under pressure, and the like. The excellent water-absorbing resin not only has to satisfy the physical properties listed above, but also needs to be industrialized. 7 [Prior Art] The component material for the water-absorbent resin known in the artisan industry is a water-decomposable powder of a powder of acrylonitrile (Japanese Patent Publication No. S 49 (1974M3,395), neutralization The powder of the temple-g-graft polymer (Japanese Patent Laid-Open Publication No. Sho 51 (19:6)-125,468) 'Saponified Ethylene Acetate_Protocol Copolymer (Japanese Patent Publication No. 1977) ·! 4,689 Acrylonitrile copolymer or propylene copolymer (曰=报昭53 (1 is called 15,959), and partially neutralized polyacrylic acid (Japan specializes in: σ昭55 (1 called 84,3〇4), etc. Powder-B-Wan guesses that the graft polymerization contains a natural polymer, which will cause decomposition of rot, so the preservation of όΓIc II; in addition, the manufacturing method is very complicated, so the preparation of today's high 'October 曰The method of using superabsorbent resin made of acrylic acid and acrylate to cross-polymerize 1351417 is the most economical, and the reason is that the acrylate copolymer raw material - propylene glycol can be quickly purchased from the market. And the obtained super absorbent resin has high water absorption capacity and low manufacturing cost It is the most general-purpose superabsorbent resin because it is inexpensive and most economical and does not cause decomposition of rot. The method of forming acrylic acid and acrylate to form a superabsorbent resin can be obtained by several known methods, such as an aqueous solution. Polymerization, reverse phase suspension polymerization, emulsion polymerization or spraying or coating of monomers onto a fibrous substrate for polymerization, etc. In these methods, reverse phase suspension polymerization and emulsion polymerization must be carried out. If the organic solvent is not effective, but if the temperature of the reaction is not effectively controlled, the organic solvent will cause the temperature of the reaction system and the pressure to increase, which may cause a fire phenomenon or even an explosion, thereby threatening the safety of the personnel at the operation site and causing Environmental pollution problems, the finished product also has the doubt of organic solvent residue. The manufacture of superabsorbent resin is carried out by aqueous solution polymerization, reverse phase suspension, polymerization, milk recording reaction or coating on fiber impurities. Polymerization and other methods must eventually be dried, and generally use (10) to • 23 (TC high temperature - Sub-drying method; however, before drying, the bulk colloid obtained by polymerization must be made into small particles by the female crushing method (except for the reverse phase suspension polymerization), and the small particle colloids are evenly dispersed in the dryer. In order to facilitate the drying. [Technical issues to be solved] Mainly in the form of perforated plates, the current industry has developed 'such as the method of crushing superabsorbent resin colloids in the use of technology, cutting knives, by extrusion screw Squeeze the slag, make it smash, a variety of methods to prevent the colloid from sticking to agglomerate after pulverization, 1351417 • Without __ soil, disperse, this _ thing uses tangled silk to select the appropriate size of talcum powder, smash into small colloid In the process of colloid, talc powder added to the fine water-based resin is used to increase the dispersibility and fluidity of the small colloid, but there are several major defects in this way: one is in the crushing Process order, due to the long-term friction of the inorganic salt ore with the cutter head, the life of the cutter is greatly shortened. Second, the mineral powder has a certain influence on the physical properties of the super absorbent resin. When the powder _ line, increasing manufacturing difficulty Arts I, the third is pink touch the body _ • health hazardous, especially open-ended process. There are other ways in the art world to improve the dispersibility of superabsorbent resins, to reduce colloidal agglomeration, or to reduce the resistance of the pulverizer cutters, such as special fair _ • No. 73576, special [Kaiping 2- Circular No. 24361 'The process of using the squeezing mechanism granules• Adding release agent, Shixia oil, sulphur dioxide or mineral powder to reduce the phenomenon of superabsorbent resin condensation; special fair __报枝_ Water solubility is not good 'even insoluble in water release agent (adhesion preventive agent) to solve this phenomenon, including _ 200~4〇〇t oil separation, high molecular weight fatty acid acetate, viscosity at 10 ~5xl〇V/Sec stone oil. However, such water-soluble release agents and even water-insoluble release agents (adhesion preventive agents) also have a serious problem - surface tension; the superabsorbent resin obtained by this method has a greatly reduced surface tension. To increase the possibility of diaper rewet. 8 9 1351417 kinds of hydrophilic surfactants usually contain an alcohol group (-0H), and have good hydrophilicity. When the amount is too low, the superabsorbent resin is more likely to have agglomeration. [Technical means for solving the problem] In order to solve the above problems, the present invention utilizes a water-soluble surface dispersing agent to assist in colloidal dispersion, and the surface-dependent water reduction can be assisted in three cases to assist in dispersing the body, and in the large colloid. In the process of making small particles, second, after the small particles are made, second, after the large colloids are made into small particles, and the small particles are made, and the surface of the water-soluble surface disperses the following: -, in order to avoid the wire © the main functional group of the superabsorbent resin - rebel (C_ reaction, the surface of the component of the side can not be alcoholic, epoxy, etc., easy to reduce the reaction of the compound, In order to avoid reaction with the carboxyl group (C00,) of the highly water-absorptive resin after ionization, the composition of the surface dispersing agent may not be: or have a metal ion salt for reading, and third, the wire tension is too low, and the surface dispersing agent is 0.5%. The surface tension of the aqueous solution should be above 25dyne/cm2. Fourth, in order to increase its 'new tension, it can add not more than 50% by weight of hydrophilic solvent to the surface dispersant, and hydrophilic organic solvents such as decyl alcohol, ethanol, and C. Alcohol, isobutanol, propane net, Ethyl ether, diethyl ether, etc. [Explanation] The water-soluble unsaturated monomer required for producing the super absorbent resin of the present invention, other than propylene I, can be used other water-soluble having a fine unsaturated double bond. Monomers, such as: mercaptopropionic acid, mazinic acid, fumaric acid, 2-propylene amide, mercapto-propyl sulphate, cis-butene, maleic anhydride, anti-sweet The anti-succinic acid needle and the like 4 can be used only in the non-special domain system, and can also be combined with a plurality of monomers - 10 ^ 51417. It is also possible to add a monomer having an unsaturated double bond and other hydrophilicity as the case may be. Such as: acrylamide, mercapto acrylamide, 2-methoxyethyl acrylate, 2-carboxyethyl methacrylate, decyl acrylate, ethyl acrylate, decyl propylene acrylamide, gasified propylene propylene The amidoxime diammonium ammonium is added in such a manner that the physical properties of the superabsorbent resin are not impaired. In the present invention, the concentration of the aqueous monomer solution is not particularly limited in the case of performing radical polymerization, but the preferred concentration is preferably controlled in weight percentage. 2〇 plus % to 55wt%, the appropriate concentration is 30wt% to 45wt% When the concentration is less than 20% by weight, the hydrogel after polymerization is too soft and sticky, which is unfavorable for mechanical processing. The added concentration is above 55 wt% by weight, close to the saturation concentration, and the pH is easy to formulate and the reaction is too fast. The reaction heat is not easy to control. The pH of the unsaturated monomer solution is not less than 5 5, and if it is less than 5 5 , the residual monomer content in the hydrogel after polymerization is too high, resulting in poor physical properties of the superabsorbent resin. The slow acid group 'should be partially neutralized to control the pH of the finished product to make it 'neutral or slightly acidic. The neutralizing agent is the nitrogen oxide or the carbonic acid compound of the gold or soil test group in the periodic table, such as : sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, hydrogencarbonate or ammonia compound; the neutralizing agent can be used alone or in combination. The decanoic acid moiety of the acid group-containing monomer is neutralized to a sodium salt or a sulphate salt or a salt salt. The concentration of the neutralization molar concentration is finely 1% to 85 md%, preferably from 1% to 1%. When the percentage of neutralization concentration is below 45m〇1%, the positive value of the finished product will be low. The positive value of the finished product will be higher than 85%%. The positive value of the finished product will be higher. The pH value of the product is not neutral or micro. When it is acidic, if it is inadvertently contact with the human body, it will not be subjected to the free silk retest. The monomer water and towel village will add water-soluble high 1351417 molecules to reduce the cost. Such water-soluble polymers such as partially saponified or fully saponified polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polypropylene decylamine, starch or starch derivatives such as thiol cellulose 'methyl methacrylate, B A polymer such as a cellulose; the molecular weight of the water-soluble polymer is not particularly limited, and among them, a preferred water-soluble polymer is starch. The partially saponified or fully saponified polyvinyl alcohol or the like may be used singly or in combination. The superabsorbent resin contains 0 to 20% by weight of the water-soluble polymer, and is added in an amount of from 0 to 20% by weight. Preferably, the enthalpy to 5% by weight is particularly preferable, and when it is added in excess of 20% by weight, the physical properties are affected, and the physical properties are deteriorated. Before the radical polymerization reaction, a radical polymerization crosslinking agent should be added to the unreacted monomer solution, and the radical polymerization crosslinking agent may be a compound having two or more unsaturated double bonds. Such as: wind; ^'_ bis (2-propenyl) amine, N, N'-methine bis acrylamide, N, N, _ decyl bis decyl acrylamide, propylene acrylate, ethylene Alcohol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimercapto acetoacetate, polyethylene glycol dimethacrylate, glycerin triacrylate, glycerol tridecyl acrylate: acid vinegar,甘_加王里氧乙炫;^Acrylic shouting tridecyl acrylate, triterpene propane plus ethylene oxide triacrylate or tridecyl acrylate, dimethanol propane tridecyl acrylate, trimethylolpropane Triacrylate, N,N,N_bis(2.propenyl)amine, ethylene glycol diacrylate, polyoxyethylene glyceryl triacrylate, diethyl ethoxylate diacrylate, dipropylene triethylene glycol For esters, etc., compounds having two or more epoxy groups, such as sorbitol polyglycidyl, may also be used. Ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol dihydrate glycerin bond, polyethylene glycol monoglycidil scale, diglycerol polyglycidil test, and the like. After the radical reaction, the superabsorbent resin can have an appropriate degree of crosslinking, and the superabsorbent resin colloid can have appropriate processability. The radical polymerization crosslinking agent may be used singly or in combination of two or more (iv). The amount of the additive 丄3.51417 of the radical polymerization crosslinked ship# is between 0.001% by weight and 5% by weight (based on the total solids of the reactants). A more suitable amount by weight is from O.Olwt% to 3% by weight. Between the additives, the hydrate is too soft and viscous under the weight percentage of O. OOlwt% after polymerization. The amount of the additive is less than 5 wt% by weight, and the water absorption is too low, which lowers the resin properties. The polymerization starts by the decomposition of the radical polymerization initiator to generate a radical. The free radical initiator may be selected from a thermal decomposition type initiator, and a suitable thermal decomposition initiator is a peroxide such as hydrogen peroxide, di-tert-butyl peroxide, guanidinium peroxide or persulfate. Salt (ammonium salt, alkali metal salt), etc., and azo compounds such as: Z2, azobis(2-lungylpropane) dihydrochloride, 2.2, _azobis(9)^-dimethyl Isobutyl hydrazine) dihydrochloride; may also be used as a redox initiator, such as: acid I1 sulfite, thiosulfate, ascorbic acid or ferrous salt; or redox The initiator and the thermal decomposition initiator are used in combination. First, the redox initiator first reacts to generate a radical, and when the radical is transferred to the monomer, the polymerization proceeds. 'A large amount is released due to the polymerization reaction. The heat increases the temperature, and when the temperature reaches the decomposition temperature of the thermal decomposition type initiator, decomposition of the second stage thermal decomposition type initiator is caused, and the entire polymerization reaction is more complete. Generally, the radical polymerization initiator is used in an amount of 0.001% by weight by weight based on the weight of the neutralized acrylate, and more suitably in the range of from 01% to 5% by weight. When the percentage is less than 0.001% by weight, the reaction is too slow to be economically advantageous. When the weight percentage is 10 wt%/〇 or more, the reaction is too fast and the heat of reaction is not easily controlled. The polymerization reaction can be carried out in a conventional batch reaction vessel or on a conveyor belt reactor. The superabsorbent resin colloid produced by aqueous solution polymerization is generally not directly dried due to excessive volume, and must be passed through a mincer. The gel system 12 (S) 1351417. into a small condensation frequency under lcm3 α, and then through the colloidal particles + spreader = on the drying » on (four) Lai dry, according to this (four), in order to reduce the screwing rod ^ squeezing the money The resistance suffered, and the dispersal of the body, the improvement is the process of granulation, the addition of people does not with the high-yield, the surface of the knife is reduced by the water. The amount of the aqueous solution of the preferred surface dispersant is preferably the weight of the water-absorbent resin colloid; however, the surface dispersing agent is limited to the aqueous solution polymerization, and the water-repellent tree obtained by the reverse-counting of the knife is turned to _, granulate or increase the water absorption. φ sex tree gelatin dispersion, fluidity, can be applied. Cloth is not broken Γ ί small plastic rags in the dry and over-the-counter, super absorbent resin scattered

^When the drying efficiency is high, the drying temperature must be increased. Once the drying temperature is lower than 夂S, the water-absorbent resin is easy to generate bubbles. After grinding, it is easy to raise the amount of fine powder of the ancient product, so that the physical properties are not Better, and reduce production capacity. 4 “The temperature of the production of deduction f 1 is suitable for the chess to be carried out by the temperature. The arch • cu is dry for too long, and it has no economic benefit. For the dry temperature test, the internal crosslinking agent is prematurely cross-linked, followed by The wire ==== can not effectively remove the unreacted residual monomer, and achieve the reduction of the addendum f, which is turned on the table top of the invention, including: the channel mixing dryer, the drum dryer , dry type, chemical bed dryer, airflow drying H and infrared dryer. The superabsorbent resin is an insoluble hydrophilic polymer, and the resin has a bridge structure of 13 (S) 14 1351417, which is generally used for the degree of modification, anti-caking property, liquid infiltration, etc. Agent, before this = = there is a polyfunctional base agent capable of reacting with an acid group in an organic solvent to disperse the superabsorbent resin and cross-link JP-A-57-44627, : 乂 处理 processing (claw edge 13_, ▲ -A-58_42602, JP-A58-117222)' Use of inorganic residue, (two 1 = mixed with jp crosslinker solution into superabsorbent resin)

r, -A-60-255814), after adding a crosslinking agent, treating the material with helium gas, 406), using an organic solvent, water, and a polyol, Table, U.S. Patent No. 69, the side of the treatment, etc.; Although the method has two t and = rate, and the absorbent material under the wire pulling force, it will cause the rotation force to drop the consequences and reduce the performance of the actual application. The crosslinking agent capable of simultaneously reacting at the time of surface treatment may be a polyhydric alcohol such as: glycerin: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, m; alcohol, three Methyl methicone, sorbitol, etc.; or polyamines such as ethylenediamine, diethylamine, diethylenediamine, polyethylenediamine; or two or more decyloxy groups may be used. Compounds such as sorbitol polyglycidol, polyglycerol polyglycidol = ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol dihydrate, glycerol Water sweet; can also make acid sub-smoke ^ such as: ethylene glycol carbonate, 4-mercapto-1,3-dioxol-2-one, 4,5-diindenyl hydrazine, monooxy Heterocyclic pentan-2-one, 4,4·didecyl-1,3·dioxol-2-one, 4-ethyl-1,3·dioxacyclonon_2· Ketone, iota, dioxane-2-phene, 4,6-didecyl-oxetan-2-one or 1,3-dioxepane-2-one . The crosslinking agent may be used singly or in combination of two or more. The appropriate amount of the crosslinking agent is between 1% and 10% by weight (based on the total solids of the reactants), and more preferably 0.005 wt%. Between 5wt〇/〇, the crosslinking agent additive amount can not show the effect below the weight percentage of OOlwt/ί), and the crosslinking agent additive amount is less than 10wt% by weight, the water absorption is too low, and the resin performance is lowered. . ▲When the surface of the parent bonding agent is applied, the surface crosslinking agent is added according to the type of the surface crosslinking agent, and the surface crosslinking agent is directly added, _ into the surface crosslinking agent aqueous solution added 'or the surface crosslinking cross-linking Ship aqueous organic solvent solution is added. Parents, organic solvents such as decyl alcohol, ethanol, propanol, isobutanol, propylene _, 曱 _, 乙 峻, etc. are not particularly limited, and can form a solution, among which methanol and ethanol are preferred (US Patent No. 6,846,665) . When the surface crosslinking agent is added, the superabsorbent resin + the inert inorganic salt powder may be added to be dispersed by the gamma solution, and the ship's powder may be sulphur, or sulphur dioxide, or oxidized, or oxidized or the like or a mixture thereof. It is made of sulfuric acid and oxidized. The ship has no _ powder _ law can be single thief combined with more than two types. The inert inorganic salt powder is added in an amount ranging from 0.005 wt% to 2 lO.Owt% by weight, wherein 〇lwt〇/〇 to 4 〇 plus % is preferred. • After the surface cross-linking agent is applied, it is heated in the range of 9 (TC to 23 〇t, so that the surface cross-linking agent can carry out the cross-linking reaction uniformly and rapidly, and the internal cross-linking agent At the same time, the cross-linking reaction is carried out to achieve the effect of the present invention. The heat treatment temperature is less than 9 〇t, and the crosslinking reaction time is too long. 'There is no economic benefit, the heat treatment temperature (10) ς = the resin is easily deteriorated and the product f is affected, and the heat treatment is mx 30 minutes to 15 G minutes. It is advisable to adjust the temperature of the heat treatment according to the surface of the surface, and the heat treatment temperature is high, and the heat treatment is short. When the temperature is low, the temperature of the treatment is long: the heat treatment can be completed by using an ordinary dryer or a heating furnace. The heat treatment apparatus suitable for the present invention includes: a channel type mixing dryer, a drum type drying 15 1351417, a table top dryer, a fluidized bed dryer, an air flow type dryer, and an infrared drying type. After heat treatment, water-insoluble fine powder is added to the superabsorbent resin, and the anti-caking treatment is carried out in order to increase the gap between the superabsorbent resin particles, so that the high-sucking tree stalk absorbs the fish gas. After the high fluidity, the water-insoluble micropowder is added directly, and the water-insoluble micropowder is adhered to the surface of the superabsorbent resin by using an adhesive; the water-insoluble micropowder includes aluminum sulfate, magnesium sulfate, aluminum oxide, oxygen, helium, and consumption. Soil, soft soil, clay, slippery territory, bentonite, activated carbon, dioxide, inorganic salt powder of titanium dioxide, and such as cellulose powder, poly!, polyethylene, polyvinyl chloride, polystyrene Organic powder The above-mentioned water-insoluble fine powder has the best effect of adding an inorganic salt powder. The inorganic salt powder may be used singly or in combination of two or more. The addition range is in the weight percentage _lwt% to 10 gamma%. Preferably, the particle size of the water-insoluble fine powder is not more than 10 mm, and the more appropriate size is less than 6 mm. The adhesive may be a polyol such as 100% by weight. : glycerol, polyethylene glycol, sorbitol, or kelang polyethyleneimine. The snail can be used alone or in combination of two or more. The appropriate amount of the additive in the adhesive is from 0 to 100% by weight to 10% by weight. %between (based on the total solids of the reactants), a more appropriate amount is between 0.005 wt% and 5 wt%, and the amount of the additive additive is not mixed with the powder at the weight percent _lwtWXT. When the adhesive weight is more than or equal to the weight percentage, the water absorption is too low, and the resin property is lowered. The object of the present invention is to increase the production efficiency and enhance the physical properties of the product by adding a dispersant to the sample to produce a powder. Insoluble in water, it can absorb 1351417 water or urine and blood. It has high retention, low residual unreacted monomer, and high-performance superabsorbent resin with high absorption rate characteristics under the pressure. The manufacturing method comprises at least: (a) a neutralization ratio in the range of 45 to 85 mol%, and a concentration of the unsaturated monomer aqueous solution in a range of 20 to 55 parts by weight; (b) high water absorption by polymerization after neutralization Sexually reversing the water, first to make a large hydrogel

The block is made into a small particle gel by a cleavage machine, and an aqueous solution of a surface dispersing agent can be added in the process; (c) the aqueous solution of the spray disintegrator is sprayed on the small hard gel to make it mixed; (d) Drying, pulverizing, screening; (e) surface cross-linking agent coating; and (0 temperature 9Gt to 2 pit heating surface modification treatment. *Shi I reverse phase ~ prepolymerization. External 'high water absorption after polymerization Resin, all need to pass π machine, ship machine or granulator shaft, 敎 block high water-absorbent resin 救 body to save its viscosity, will hinder the squeeze _ shovel shovel machine, affect (four) M turn '- too large resistance Even the frequency hopping will occur. Before drying, even (4) small particles of resin in the dry domain are also important things to gather into a group, so that the fine fruit turns, = all, pure high-capacity resin accumulation state, thus affecting the follow-up The process of the ^Guangcheng part of the group is still unfinished, will make it face, pink (10) 仃 'If you improve the dryness to solve this problem, when you are dry and dry, the ancient 哄 ^,,.' The amount of powder in the field increases. When the superabsorbent resin is at a high temperature, the moisture inside the W 7 resin is easily lost because it is too late to escape, and the 1351417 is internally Bubbles, bubbles _ many, squeezing, grinding, fine powder, so that the amount of superabsorbent resin dust increases; the amount of fine materials on the environment and the impact of bio-rentation, especially in the air The suspended particles enter the lungs through the respiratory tract, • the opportunity to attach the suction path lesions' and when the amount of fine powder is more, the size of the particles is suitable for commercial use.

The amount of water-absorbent resin is reduced. The more the amount of sputum recovered, the lower the production efficiency and the higher the cost. [Embodiment] In order to visit the hair _ fine powder, the following steps can be performed. Firstly, the monomer is neutralized and added to the superabsorbent resin hydrogel, and the gum and the dispersant are added to the crucible (the product of the company, the ship is known as the type (10)), and Including - to the array of tools and porous discs, the hole diameter is 3 至 leg to 3 sides, 'the other 2 has current _ device, can control the body resistance of the screw. After the dust squeezing machine, a roller granulator is connected, and the small granules of the squeezing waste are directly introduced into the roller towel, and the spraying or inflow device of the sub-fourth is added thereon to increase the grading New Zealand, and at the exit, the inspection of the dispersing time of the g-nana body is carried out. The rest of the hybrid belt is transported to the dry miscellaneous (the product of the mouth of the company is DV70 type; or the product of the Meridian company, model For ^tjcnjs type 1351417), dry it with 13 (M耽 for complete drying, pulverize the dried superabsorbent resin particles, and calculate the distribution ratio of each particle size by standard __ to detect different money temperature The bribes are renewed (four) fresh, and the money is affected by the taste. The invention _dispersion_method, take the super absorbent resin age before drying, i〇〇g 'put it into length, width, height 5cm, 5cm , i〇cm transparent acrylic (the upper and lower ends of the tube are open), in the method of pressure code, on the high-absorbing resin _ to force Up_ 1G seconds, _ gram force After the diagnosis and the inspection, the observation is tight and the high suction _ is, and the time is equal to the time on the ground (4). According to the edaNa test, the pine wsp22G 2 (峨·(4) method; the bottom plate of the bottom plate is placed in the vibrator, the screen is arranged in the order of the smaller mesh, the vibrator is activated, and the amplitude is 1.0. After mm '1 () minutes, the vibrator is stopped, and the high-yield resin of the same particle size is sorted and weighed, and the distribution ratio of each particle control is calculated. /, Particle size distribution ratio (% ) = high suction in the screen ^ all screens *1〇〇〇/0 The invention is designed to facilitate the evaluation of screening performance, and the high water absorption is 1Λ/:, the primary T is less than

Um (JIS standard screen is MOmesh) is regarded as fine powder, and it is used to determine the influence of drying temperature on fine powder. The 柘1351417 will affect the performance of the urinary retraction due to the surface tension value. To demonstrate the high surface tension value of the superabsorbent resin of the present invention, the surface tension value is measured by the surface tension meter Processor Tensi〇meter K100; The initial weighing weight of 55g of superabsorbent resin is placed in a beaker, 4 〇ml 〇9% 9% saline is added, the magnet rotor is held at 600-for 3 minutes, and then 〇.9% liquid is transferred to the crepe paper to the surface. The tension meter detects the surface tension of the filtrate. The retention force (CRC) of the present invention is determined by the tea bag test method, and the highest value and the lowest value are removed after five measurements, and the average value is taken; 2 g of the super absorbent resin is placed in the tea bag' and soaked 〇 〇 9% NaC1 aqueous solution for 2 〇 minutes, then the soaked tea bag was centrifuged in a centrifuge (diameter 23 cm, speed 14 〇〇 ah) three minutes after weighing. The value obtained is first obtained by subtracting the blank group weight of the unfilled superabsorbent resin (operating in the same step) and dividing by the weight of the polymer to obtain the retention value. The determination of the low residual body is the first step of the Hunan liquid granule analyzer (HpLC). The 500g 咼 water-absorbent resin is placed in a 15〇cc conical flask, and the 524·524% Naa aqueous solution l〇yg and 2cm are added. One stirrer, mix at a speed of % rpm for one hour, add 20% A12 (S〇4) 3 aqueous solution 5g 'reuse 2μιη filter paper, filter the filtrate into liquid chromatograph, analyze the signal and The amount of residual mass can be obtained by comparing the calibration curves. The invention is illustrated by the following examples; however, the patents and technical scope of the invention are not limited by these examples. [Examples] Example 1: 1351417 1) Take 8〇2g of 48% aqueous solution of hydrogen hydroxide and 1〇69 2g of water into a 4〇〇〇cχ round bottle. Slowly add 330g of acrylic acid and keep it in the bottle. The pH of the water-soluble unsaturated monomer after the neutralization of the temperature of the reaction system below 40 ° C is 12.6. After standing for 5 minutes, 660 g of acrylic acid was further added to the partially neutralized water-soluble unsaturated monomer, and the pH of the water-soluble unsaturated monomer after complete neutralization was 5.6. At this time, a water-soluble unsaturated monomer concentration of 42% by weight aqueous solution was obtained, in which 70 mol/〇 (mole ratio) of the acrylic acid was partially neutralized to sodium acrylate. 2) Add 1.518 g of n,N'-methine bis acrylamide to the water-soluble unsaturated monomer solution and maintain the temperature at about 20 °C. ) Forced into 0.528 g of dual gas water ' 6.62 g of sodium hydrogen sulfite and 6.62 g of persulfate was recorded to initiate the reaction. The gel produced by the reaction was chopped by a cutter mill, and a nonionic surface dispersant-poly, ethylene glycol distearate was added at this time (Zhongri Synthetic Chemical Co., Ltd. - A Division A) k for) 'The concentration is 1 〇 / 〇, 1 〇 /. The amount of dispersing agent used for pulverizing colloid is 20% 'observe the change of extruder current (please refer to Table 1). Pour the above pulverized colloid into the granulating drum, and add 1% polyethylene glycol at this time. Hard acetic acid vinegar water solvent, 1% dispersing agent used in the pulverized colloid is 2〇%, after mixing in the cylinder for about 5 minutes, take out the change of colloid dispersion time to see the table 1). Ming 6) Dry at 130 ° C for 2 hours. The amount of the fine powder obtained by the vibrator is 10 minutes. The ratio of the amount of fine powder is 0.02% (please See Table 1). 8) The superabsorbent resin obtained by grinding is larger than the super absorbent resin', and the residual monomer test, 21 1351417 " 22 r retention force (CRC) test and surface tension test (see Table 1) are performed. Example 2: 1) Repeat steps 1) to 8) of Example 1, but change the concentration of polyethylene glycol distearate to 10% '10% dispersant to reduce the amount of pulverized gel to 5 〇/ Hey. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. ^ Example 3: 1) Repeat Example - Step 1) to 8), but add 1% ethanol to an aqueous solution of i% polyethylene glycol di-hard acetic acid vinegar. • 1 extruder current, colloidal dispersion time, fine powder, residual monomer, retention and surface tension values, as shown in Table 1. Example 4: • Repetitive Example 1 step, but non-ionic surface dispersant - polyethylene glycol di-hard acetate, 'replaced with ionic surface dispersant _ polyethylene glycol hyaluronic acid ammonium sulfate Salt (provided by Sino-Japanese Synthetic Chemical Co., Ltd.). 22 1 Its extruder cake, colloidal dispersion _, women's amount, residual monomer, retention and surface tension values, as shown in Table 1. Example 5:) Heavy-duty four steps 1)~2) 'But the ionic surface dispersant-polyethylene glycol 1351417 burning base __lining changed to 1G%, job __ broken colloid = dosage Both are reduced to 5%. 2) The squeezing current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. , Example 6: • Alcohol-based sulphuric acid sulphuric acid n Repeat Example 4 steps 1) ~ 2), but in! 1 〇 / 0 ethanol was added to the % polyethyl bromide solution. 2) The extruder current, the colloidal fraction, the main pulverizing time, the fine powder, the residual monomer, the holding force and the surface tension value, as shown in Table 1. Example 7: 1) Repetitive Example - Step υ ~ 8), but non-official surface dispersant · polyethylene glycol two hard _, changed to ionic surface dispersant - dicetic acid dioctane (four) Sodium (provided by Synthetic Chemical Co., Ltd.), 2) The pressure of the weaving machine, the time of the slug, the amount of fine powder, the residual monomer, the retention force and the surface tension value. Show. Example 8:) The seven steps of resetting the actual conditions, but the ionic surface dispersing agent _ succinic acid dioxin @ 曰 was changed to 1% by sodium, and the usage of the 〇% dispersed drill pulverized colloid was reduced to 5%. Fine powder amount, residual monomer, retention 2) extruder current, colloidal dispersion time, 23 24 241351417 and surface tension values, as shown in Table 1. Example 9: 1) Example 7, steps 1) to 2) were repeated, but 1% ethanol was added to 1% aqueous sodium dioctyl succinate sulfonate solution. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 1: 1) Repetitive Example 1 Steps 1) to 8), but 1% polyethylene glycol distearate aqueous solvent, changed to 70 ° / ◦ polyethylene glycol distearate aqueous solvent . 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 2: 1) Repeat steps 1) to 8) of Example 1, but will be 1 ° /. The polyethylene glycol distearate aqueous solvent is changed from 20% to 40% when the step 3) is pulverized and the step 4) is granulated. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 3: 24 !3.51417 1) Repeat Example 1 step l) ~ 8), but 1% polyethylene glycol distearate aqueous solvent, changed to 1% stearic acid town with high-valent metal ions Water Solvent (provided by Sino-Japanese Synthetic Chemical Co., Ltd.) β 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 4: _ 丨) Repeat steps 1) to 8) of Example 1, but 1% polyethylene glycol distearate aqueous solvent, and changed to a pure water solvent. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. Comparative Example 5: 1) Repeat Example - Steps 1) to 8), but 1% polyethylene glycol di-hard vinegar water-soluble agent, changed to no solvent. 2) The extruder current, colloidal dispersion time, fine powder amount, residual monomer, holding force and surface tension value are shown in Table 1. 25 261351417 Table 1 Extruder Current (A) Colloid Dispersion Time (sec) Retention (g/g) Surface Tension (dyne/cm2) Fine Powder (8) Residual Monomer (ppm) Example 39 18.4 41.2 65.6 2. 02 340 Example 38 15.6 40.6 59.4 1.68 306 Example 39 19.2 41.4 66.7 2.12 356 Example 40 15.7 42.0 63.3 1.89 412 Example 39 13.4 41.4 57.6 1.54 387 Example 41 16.9 42.3 65.4 2.03 442 Example 38 19.7 41.8 62.3 2.32 387 Implementation Example 38 17.4 41.1 56.3 1.88 334 Example 39 20.4 40.9 64.1 2.98 398 Comparative Example 37 13.6 41.6 44.3 1.44 344 Comparative Example 48 20.3 39.4 49.3 3.54 367 Comparative Example 39 18.6 36.8 63.1 1.87 382 Comparative Example 73 38.9 41.6 70.2 5.12 612 Comparative Example 58 33.2 40.9 70.7 4.67 563 26 271351417 [Simple description of the diagram] [Description of main component symbols]

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Claims (1)

Amendment page 10, August 9th, the patent application scope h: 22 ί5 ί monomer aqueous solution preparation method for the preparation of superabsorbent resin, the square (4) neutralization ratio is 45 to 85 mol% of the _, unsaturated The concentration of the aqueous monomer solution is polymerized in a range of 20 to 55 parts by weight to form a superabsorbent resin hydrogel; (6) in the process of pulverizing the superabsorbent hydrogel formed after polymerization into a small particle gel. An aqueous surface dispersant solution is added in an amount of from 0.005 wt/〇 to 50 wt% by weight of the superabsorbent resin hydrogel; (c) dried, pulverized, and sieved.